CN101759979B - PC/ABS material composition for relieving yellow discoloration - Google Patents
PC/ABS material composition for relieving yellow discoloration Download PDFInfo
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- CN101759979B CN101759979B CN 200810207585 CN200810207585A CN101759979B CN 101759979 B CN101759979 B CN 101759979B CN 200810207585 CN200810207585 CN 200810207585 CN 200810207585 A CN200810207585 A CN 200810207585A CN 101759979 B CN101759979 B CN 101759979B
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Abstract
The invention discloses a PC/ABS material composition for relieving the yellow discoloration, which is prepared from the following ingredients in percentage by weight: 10 to 60 parts of acrylonitrile-butadiene-styrene graft copolymers, 30 to 85 parts of polycarbonate, 0 to 10 parts of acrylics graft rubber, 0.25 to 0.88 parts of coloring agents, 0 to 1 part of antioxidizers and 0 to 1 part of light stabilizers. Yellow dyes without light illumination resistance performance exist in a dye system, and the dyes can not influence the whole coloring process of plastics in the plastic coloring process, but in the light illumination process, the dyes gradually fade, the PC/ABS materials carry out yellow discoloration in the light illumination process, so the two mutually inconsistent processes have the mutual counteraction effect, and the color aberration of the whole PC/ABS composition is reduced after the light illumination. At the same time, the mechanical property of the composition material is not obviously reduced.
Description
Technical field
The present invention relates to a kind of PC/ABS material compositions, be specially a kind of PC/ABS material compositions that has improved yellow discoloration, solved modified plastics illumination after color cause the problem that cancerates.
Background technology
The PC/ABS plastics have good thermotolerance, and impact and good processibility are widely used in the automotive upholstery component.Plastic material is felt influence very greatly in long-term sunshine (particularly UV-light) postradiation color and glossy variation to the performance and the outward appearance of automotive upholstery.In general; The automobile original equipment manufacturer (OEM) all is provided with the light radiation requirement of harsh automotive upholstery material color; The PV1303 interior material illumination standard of Volkswagen for example; Just require interior material after 3～10 cycles of illumination (common 5 cycles), the colour fastness grade is necessary >=and 4 grades.
But; Because the ABS material in the PC/ABS material has two keys to exist; Under the condition of illumination, be very easy to the generating material xanthochromia, this influences bigger concerning the whole colour system of PC/ABS material, has also aggravated the color aberration of PC/ABS plastics after illumination simultaneously more.
Usually the method that solves the variable color of polymer materials illumination ageing is to add various photostabilizers; But because the chemicals-resistant corrosive nature of polycarbonate is poor; And processing temperature usually can be near 300 ℃; So many photostabilizers, particularly to alleviating the very effective hindered amine light stabilizer of polymer materials material illumination ageing variable color, like Tinuvin 770; Under so high processing temperature, very easily cause the reduction of polycarbonate molecular weight, thereby cause the rapid deterioration of the PC/ABS mechanical property of materials.
Summary of the invention
The object of the invention aims to provide a kind of PC/ABS material compositions that improves yellow discoloration, to solve and to improve PC/ABS causes aberration because of the material xanthochromia under illumination condition problem.
The object of the invention can be realized through following technical scheme:
A kind of PC/ABS material compositions that improves the xanthiochromatic change comprises: acrylonitrile-butadiene-phenylethene grafted copolymer (ABS), polycarbonate, esters of acrylic acid graft rubber, tinting material, oxidation inhibitor and photostabilizer.Described acrylonitrile-butadiene-phenylethene grafted copolymer is the 10-60 weight part; Polycarbonate is the 30-85 weight part, and the esters of acrylic acid graft rubber is the 0-10 weight part, and tinting material is the 0.25-0.88 weight part; Oxidation inhibitor 0-1 weight part, photostabilizer 0-1 weight part; In the described tinting material, white titanium pigment is the 0.1-0.3 weight part; Coffee is red to be the 0-0.06 weight part; Orange red is the 0-0.1 weight part; Inorganic Huang is the 0.08-0.17 weight part; The dyestuff Huang is the 0.02-0.12 weight part; Carbon black is the 0.05-0.13 weight part.
The ABS that described acrylonitrile-butadiene-phenylethene grafted copolymer (ABS) resin is produced for the continuous bulk polymerization method.
Described polycarbonate is the bisphenol A-type aromatic copolycarbonate.
Described esters of acrylic acid graft rubber is that the methacrylate butadi ene styrene copolymer with nucleocapsid structure meets skill rubber MBS.
Described tinting material is white titanium pigment, inorganic Huang, dyestuff is yellow, orange red, coffee is red and carbon composition.
Described oxidation inhibitor is the mixture of Hinered phenols antioxidant and phosphite ester kind antioxidant.
Described photostabilizer is the benzotriazole category light absorber.
Described compsn also can comprise thermo-stabilizer, static inhibitor and lubricant etc.
The yellow dyes that a lot of light fugitive photographs are arranged in dye system, and these dyestuffs do not influence the whole dyeing course of plastics in the process of coloring plastic.But after illumination; Since the characteristic of this yellow dyes light fugitive photograph, in the process of illumination, will fade gradually (being that yellow weakens gradually), and xanthochromia will take place in the PC/ABS material in the process of illumination; These two kinds of conflicting processes can play the effect of cancelling out each other; The color aberration of whole PC/ABS compsn after illumination reduced, and simultaneously, the significant reduction do not take place in the mechanical property of composition material yet.So, through selecting suitable yellow dyes system and consumption, can reach PC/ABS and after illumination, reach variable color class 4 level, finally meet the requirement of the color aberration of automotive material after illumination.
Embodiment
To combine specific embodiment below, the present invention is described further, but said embodiment only is used to explain the present invention rather than restriction the present invention.
Embodiments of the invention adopt following material:
Polycarbonate, U.S. Dow chemical company, trade mark Calibre 201-10,
ABS, U.S. Dow chemical company, trade mark Magnum 342EZ,
Methacrylate butadi ene styrene copolymer meets skill rubber MBS, Rohm-Hass company, and EXL-2691A,
White titanium pigment, U.S. KMG company, trade mark CR-834,
Inorganic Huang, BASF Aktiengesellschaft, trade mark K2001,
Dyestuff is yellow, Bayer A.G, and trade mark P120,
Orange red, Switzerland Clariant company, trade mark 72H4GL01,
Coffee is red, BASF Aktiengesellschaft, and trade mark K2795,
Carbon black, Switzerland Clariant company, the trade mark 3620,
Oxidation inhibitor, the mixture of hindered phenol and phosphite ester kind antioxidant, Cytec company, Cyanox 2777,
Photostabilizer, benzotriazole category light absorber, U.S. Cytec company, trade mark UV-5411.
The product performance testing method:
Melting index: press the ISO1133 method, 260 ℃, test under 5 kilograms of load.
Notched Izod impact strength: press the ISO179 method, the sample of 4 mm thick.
Vicat temperature: press the ISO306B method, the sample of 4.0 mm thick.
The xenon lamp accelerated deterioration: by the PV1303 of Volkswagen method, irradiation time is 5 cycles, measures Δ L, Δ a, Δ b value, and Δ E is through calculating gained.
Below provide embodiments of the invention, and further set forth the present invention.
Embodiment 1-5 and comparative example 1
After mixing by proportion of composing in the table 1, join in twin screw extruder (screw diameter 35mm, the length-to-diameter ratio L/D=36) main barrel through exsiccant PC resin, ABS, esters of acrylic acid graft rubber, tinting material and other auxiliary agent.Each section of main barrel controlled temperature (exporting from charging opening to head) is respectively 210 ℃, 240 ℃, 260 ℃, 260 ℃, 250 ℃, and the twin screw rotating speed is 300 rev/mins, and the extruded stock bar obtains product through tank cooling back pelletizing.Said product is injection molded into standard batten with plastic-injection moulding machine in 85 ℃ of dryings after 5 hours in convection oven, 250 ℃ of injection temperatures.The batten of injection formed is in 50% relative humidity, and performance test is carried out in 23 ℃ of placements at least after 24 hours.Test result is seen table 1.
Table 1
| Form | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| PC | 60 | 60 | 60 | 60 | 60 |
| ABS | 35 | 35 | 35 | 35 | 35 |
| MBS | 5 | 5 | 5 | 5 | 5 |
| White titanium pigment | 0.2 | 0.1 | 0.2 | 0.2 | 0.3 |
| Inorganic Huang | 0.17 | 0.08 | 0.12 | 0.14 | 0.08 |
| Coffee is red | 0.05 | 0.05 | 0.05 | 0.06 | |
| Dyestuff is yellow | 0.02 | 0.08 | 0.05 | 0.12 | |
| Orange red | 0.03 | 0.04 | 0.1 | ||
| Carbon black | 0.1 | 0.05 | 0.1 | 0.1 | 0.13 |
| Oxidation inhibitor | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Photostabilizer | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 |
| Test result | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Melting index (g/10min) | 23.0 | 22.8 | 23.5 | 23.8 | 23.6 |
| Notched Izod impact strength (kJ/m 2) | 55.0 | 56.1 | 54.8 | 54.5 | 55.6 |
| Vicat temperature (℃) | 117.0 | 116.2 | 116.6 | 116.8 | 116.8 |
| 3 cycles of illumination (Δ E) | 2.44 | 1.97 | 1.88 | 1.76 | 1.68 |
| 5 cycles of illumination (Δ E) | 4.92 | 2.46 | 1.93 | 1.96 | 1.80 |
The PC/ABS embodiment that is made by the visible the present invention of table 1 is after 3 cycles of illumination and 5 cycles; Its aberration Δ E obviously is superior to PC/ABS comparative example 1; Meet the requirement after the automotive interior material illumination; And physical and mechanical properties, as: melting index, notch shock, vicat temperature, compare no significant difference with comparative example.
Embodiment 6-9
After mixing by proportion of composing in the table 3, join in twin screw extruder (screw diameter 35mm, the length-to-diameter ratio L/D=36) main barrel through exsiccant PC resin, ABS, esters of acrylic acid graft rubber, tinting material and other auxiliary agent.Each section of main barrel controlled temperature (exporting from charging opening to head) is respectively 210 ℃, 240 ℃, 260 ℃, 260 ℃, 250 ℃, and the twin screw rotating speed is 300 rev/mins, and the extruded stock bar obtains product through tank cooling back pelletizing.Said product is injection molded into standard batten with plastic-injection moulding machine in 85 ℃ of dryings after 5 hours in convection oven, 250 ℃ of injection temperatures.The batten of injection formed is in 50% relative humidity, and performance test is carried out in 23 ℃ of placements at least after 24 hours.Actual test result is seen table 2.
Table 2
| Form | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| PC | 30 | 50 | 65 | 85 |
| ABS | 60 | 45 | 35 | 10 |
| MBS | 10 | 5 | 0 | 5 |
| White titanium pigment | 0.2 | 0.2 | 0.2 | 0.2 |
| Inorganic Huang | 0.14 | 0.14 | 0.14 | 0.14 |
| Coffee is red | 0.06 | 0.06 | 0.06 | 0.06 |
| Dyestuff is yellow | 0.05 | 0.05 | 0.05 | 0.05 |
| Orange red | 0.04 | 0.04 | 0.04 | 0.04 |
| Carbon black | 0.1 | 0.1 | 0.1 | 0.1 |
| Oxidation inhibitor | 0.5 | 0.5 | 1 | |
| Photostabilizer | 0.5 | 0.5 | 1 | |
| Test result | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Notched Izod impact strength (kJ/m 2) | 42.1 | 56.1 | 61.3 | 55.2 |
| Vicat temperature (℃) | 106 | 112 | 122 | 131 |
| 3 cycles of illumination (Δ E) | 1.74 | 1.75 | 1.59 | 1.70 |
| 5 cycles of illumination (Δ E) | 1.91 | 1.86 | 1.88 | 1.95 |
Visible by table 2; The PC/ABS compsn that makes by the present invention; Aberration Δ E≤2 behind the xenon lamp aging show that this alloy material has excellent anti-ultraviolet radiation performance, can meet the uvioresistant requirement of colour fastness>=4 after the accelerated deterioration of the interior material PV1303 of Volkswagen standard xenon lamp grade.
PC/ABS compsn of the present invention has excellent uvioresistant performance and mechanical property, can be used for making various inner and outer decorative parts of automobile, like automobile door plate, center armrest, back-mirror housing etc.
Claims (7)
1. one kind is improved the PC/ABS material compositions that xanthiochromatic becomes; By weight, its composition and proportioning are: acrylonitrile-butadiene-phenylethene grafted copolymer is the 10-60 weight part, and polycarbonate is the 30-85 weight part; The esters of acrylic acid graft rubber is the 0-10 weight part; Tinting material is the 0.25-0.88 weight part, oxidation inhibitor 0-1 weight part, photostabilizer 0-1 weight part;
In the described tinting material, white titanium pigment is the 0.1-0.3 weight part; Coffee is red to be the 0-0.06 weight part; Orange red is the 0-0.1 weight part; Inorganic Huang is the 0.08-0.17 weight part; The dyestuff Huang is the 0.02-0.12 weight part; Carbon black is the 0.05-0.13 weight part.
2. a kind of PC/ABS material compositions that xanthiochromatic becomes that improves according to claim 1 is characterized in that: the ABS that described acrylonitrile-butadiene-phenylethene grafted copolymer is produced for the continuous bulk polymerization method.
3. a kind of PC/ABS material compositions that xanthiochromatic becomes that improves according to claim 1, it is characterized in that: described polycarbonate is the bisphenol A-type aromatic copolycarbonate.
4. a kind of PC/ABS material compositions that xanthiochromatic becomes that improves according to claim 1, it is characterized in that: described esters of acrylic acid graft rubber is that the methacrylate butadi ene styrene copolymer with nucleocapsid structure meets skill rubber MBS.
5. a kind of PC/ABS material compositions that xanthiochromatic becomes that improves according to claim 1, it is characterized in that: described oxidation inhibitor is the mixture of Hinered phenols antioxidant and phosphite ester kind antioxidant.
6. a kind of PC/ABS material compositions that xanthiochromatic becomes that improves according to claim 1, it is characterized in that: described photostabilizer is the benzotriazole category light absorber.
7. a kind of PC/ABS material compositions that xanthiochromatic becomes that improves according to claim 1, it is characterized in that: described compsn also comprises thermo-stabilizer, static inhibitor and lubricant.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101967274A (en) * | 2010-10-11 | 2011-02-09 | 余林华 | Permanent antistatic polycarbonate (PC)/acrylonitrile-butadiene-styrene (ABS) composite material and preparation method thereof |
| CN102558817B (en) * | 2011-12-30 | 2014-05-07 | 深圳市科聚新材料有限公司 | Polycarbonate decoloration master batch, preparation method thereof and application thereof |
| CN103881349A (en) * | 2013-12-28 | 2014-06-25 | 上海普利特复合材料股份有限公司 | Highly weather-resistant colored polycarbonate-acrylonitrile-butadiene-styrene resin blending material and preparation method thereof |
| CN104479327B (en) * | 2014-12-15 | 2016-06-01 | 上海锦湖日丽塑料有限公司 | A kind of PC/ABS composition and its preparation method improving air-conditioning panel photoetch phenomenon |
| CN104559116B (en) * | 2015-01-19 | 2017-01-04 | 苏州银禧科技有限公司 | A kind of controllable high whiteness PC/ABS alloy material and preparation method thereof |
| CN107043516B (en) * | 2016-12-26 | 2019-07-26 | 上海金山锦湖日丽塑料有限公司 | With the dark heat-proof ABS resin composition for improving weatherability |
| CN109467900B (en) * | 2018-09-18 | 2020-11-24 | 江苏金发科技新材料有限公司 | PC/ABS composite material easy to be boiled and dyed and preparation method thereof |
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| CN101168614A (en) * | 2006-10-25 | 2008-04-30 | 上海普利特复合材料有限公司 | Flame-proof ultraviolet-resisting PC/ABS composition |
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| CN101168614A (en) * | 2006-10-25 | 2008-04-30 | 上海普利特复合材料有限公司 | Flame-proof ultraviolet-resisting PC/ABS composition |
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Effective date of registration: 20181227 Address after: 402560 No. 18 Longyun Road, Pulu Industrial Park, Tongliang County, Chongqing Co-patentee after: Shanghai Pret Compound Material Co., Ltd. Patentee after: CHONGQNG PRET NEW MATERIAL CO., LTD. Co-patentee after: ZHEJIANG PRET NEW MATERIAL CO., LTD. Address before: 200081 2nd Floor, 421 Lane, Siping Road, Hongkou District, Shanghai Patentee before: Shanghai Pret Compound Material Co., Ltd. |